KR20150078316A - Thermoplastic resin composition having improved impact resistance - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition having excellent impact resistance and, more specifically, relates to a thermoplastic resin composition suitable for exterior materials of various home appliances and electronic products due to greatly enhanced impact resistance, heat resistance, and external appearance by comprising a rubber-modified vinyl-based graft copolymer in which a functional group is grafted, an aromatic vinyl-cyanide vinyl-based copolymer, and a polyester resin.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition having excellent impact resistance,

The present invention relates to a thermoplastic resin composition having excellent impact resistance, and more particularly, to a styrene-based resin composition suitable for use as a cover material for various home appliances and electronic products by significantly improving impact resistance, heat resistance and appearance.

Generally, ABS (acrylonitrile-butadiene-styrene) resins are widely used in automobiles, electric and electronic devices, and automotive parts due to their physical properties such as impact resistance, styrene processability, moldability, colorability, stiffness and chemical resistance of acrylonitrile, Office equipment, household appliances, toys, and stationary. When applied to automobile parts, these ABS resins often have a large size of molded parts, are often bonded or assembled with metal parts, and are exposed to an external environment with severe climate change. Therefore, mechanical properties such as impact resistance and chemical resistance are required to be improved.

Although the conventional ABS (acrylonitrile-butadiene-styrene) resin has been tried to improve the impact resistance and the chemical resistance by adjusting the content ratio of the acrylonitrile block, the butadiene block and the styrene block, it has not been sufficient. To solve this problem, a polyester resin having excellent chemical resistance was blended, but the compatibility with the polyester resin was poor and the physical properties were deteriorated.

Korean Patent Laid-Open Publication No. 2013-0067516 (Patent Document 1) discloses a thermoplastic ABS resin composition having an impact strength improved by adding an alkyl acrylate copolymer having a modified polyester resin and an olefin block.

Korean Patent Laid-Open Publication No. 2012-0075085 (Patent Document 2) discloses a thermoplastic resin composition that improves compatibility and improves impact resistance by using a compatibilizing agent having a maleimide group.

These documents disclose a compatibilizing agent such as an alkyl acrylate copolymer having an olefin block or a copolymer containing a maleimide group in order to improve the compatibility between the ABS resin and the polyester resin, There is still a problem that defects such as a flow mark and the like appear conspicuously on the surface of the substrate.

Korean Patent Publication No. 2013-0067516 (2013.06.25) Korea Open Patent No. 2012-0075085 (July 6, 2012)

In order to solve the above problems, it is an object of the present invention to provide a thermoplastic composition having improved impact resistance, heat resistance and appearance as well as moldability. More specifically, the bonding between the aromatic vinyl-cyanide vinyl copolymer and the polyester resin is relatively reduced while inducing the bonding between the rubber-modified vinyl-based graft copolymer in which the functional group is grafted and the polyester resin And which is improved in impact resistance and appearance without deteriorating the heat resistance of the thermoplastic resin composition.

It is another object of the present invention to provide a molded article having excellent impact resistance and mechanical strength and improved appearance characteristics from the thermoplastic resin composition.

In order to achieve the above object, the present invention provides a rubber-modified vinyl-based graft copolymer comprising (A) a grafted functional group, (B) an aromatic vinyl-cyanide vinyl copolymer; And (C) a polyester resin. The present invention also relates to a thermoplastic resin composition having excellent impact resistance.

The thermoplastic composition comprises 10 to 40% by weight of a rubber-modified vinyl-based graft copolymer (A) grafted with a functional group, 40 to 60% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) To 50% by weight.

The rubber-modified vinyl-based graft copolymer in which the functional group is grafted is obtained by copolymerizing 30 to 70% by weight of a rubber-like polymer containing a functional group with 30 to 70% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound Nitrile-butadiene-styrene graft copolymer (g-ABS).

The rubbery polymer containing the functional group may contain 5 to 60% by weight of isoprene containing at least one functional group selected from a hydroxyl group, an epoxy group, an acryl group, a sulfonyl group, a nitro group, an amide group and a maleic anhydride group, % ≪ / RTI > copolymer.

The aromatic vinyl-cyanide vinyl copolymer (B) is obtained by copolymerizing a copolymer of styrene and acrylonitrile, a copolymer of? -Methylstyrene and acrylonitrile, and a copolymer of styrene,? -Methylstyrene and acrylonitrile Species or two or more species can be selected.

The aromatic vinyl-cyanide vinyl copolymer (B) may have a weight average molecular weight of 80,000 to 120,000 g / mol.

The polyester resin (C) may be at least one selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT) and polycyclohexyleneterephthalate One or more species may be selected.

The intrinsic viscosity of the polyester resin (C) may be 0.5 to 1.1 g / dl.

The thermoplastic resin composition may contain at least one selected from the group consisting of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, a colorant, , An additive selected from the group consisting of antiwear agents, ultraviolet absorbers, ultraviolet screening agents, and mixtures thereof.

In order to accomplish the above object, the present invention relates to a molded article produced from the composition described above.

The molded article may satisfy the following formulas (1) to (3).

10? L? 30 [Formula 1]

50 ≤ IZOD ≤ 80 [Formula 2]

1.0??? E? 3.0 [Formula 3]

In the above Equation 1, L is the black index value according to the ASTM D1925 standard, and IZOD is the IZOD impact strength (kgf · cm / cm) according to the ASTM D256 standard. The change in chromaticity of the specimen due to the retention of 10 minutes in the injection machine at the time of injection.)

The thermoplastic resin composition according to the present invention is not only excellent in impact resistance, heat resistance and mechanical strength, but also has a merit that the amount of generated gas is reduced due to the reduction of the reaction of the matrix, thereby remarkably improving the appearance characteristics.

Further, the thermoplastic resin composition according to the present invention is advantageous in that it has excellent flowability and moldability without adding a compatibilizing agent.

Accordingly, there is an advantage that it is possible to provide excellent surface and physical properties as a jacket of various electrical and electronic products which require simultaneously impact resistance, processability and appearance characteristics.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.

The inventors of the present invention have studied to develop a thermoplastic resin composition having excellent impact resistance and appearance, and as a result, found that a rubber-modified vinyl-based graft copolymer in which a functional group is grafted, an aromatic vinyl-cyanide vinyl copolymer and a polyester resin The present inventors have surprisingly found that excellent impact resistance, heat resistance and mechanical strength are exhibited, and that the gas generation is reduced due to the reduction of the reaction of the matrix, and the surface properties are remarkably improved, thereby completing the present invention.

The thermoplastic resin composition having excellent impact resistance of the present invention may comprise (A) a rubber-modified vinyl-based graft copolymer having a grafted functional group, (B) an aromatic vinyl-cyanide vinyl copolymer and (C) have.

Hereinafter, each component will be described in more detail.

(A) Functional group Grafted  Rubber degeneration Vinyl-based Graft  Copolymer

The rubber-modified vinyl-based graft copolymer grafted with a functional group according to an embodiment of the present invention can improve the impact strength and coloring property in combination with other components in the composition.

The rubber-modified vinyl-based graft copolymer in which the functional group of the present invention is grafted can be produced by graft-polymerizing a mixture containing a rubber-like polymer containing a functional group, an aromatic vinyl compound and a vinyl cyanide compound.

For example, 30 to 70% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized by emulsion polymerization in the presence of 30 to 70% by weight of a rubbery polymer containing a functional group to obtain a rubber-modified vinyl-based graft copolymer Can be produced.

At this time, the rubber-like polymer containing the functional group may have an average particle diameter of 0.1 to 1.0 占 퐉. Preferably, when the average particle diameter is 0.2 to 0.6 mu m, the impact resistance and the compatibility can be improved.

The functional group may be selected from at least one of a hydroxyl group, an epoxy group, an acryl group, a sulfonyl group, a nitro group, an amide group and an anhydrous maleic acid group.

The rubbery polymer containing a functional group according to an embodiment of the present invention may be a rubbery polymer containing a functional group such as a polybutadiene rubber, an acrylic rubber, an ethylene / propylene rubber, a styrene / butadiene rubber, an acrylonitrile / butadiene rubber, a polyisoprene rubber, Ethylene-propylene-diene terpolymer (EPDM), and polyorganosiloxane / polyalkyl (meth) acrylate rubber composite may be used. More specifically, polyisoprene rubber or polybutadiene rubber containing the above-mentioned functional groups can be used.

The aromatic vinyl compound in the mixture to be graft-polymerized to the rubbery polymer may be at least one selected from the group consisting of styrene, C ₁ -C ₁₀ alkyl-substituted styrene, halogen-substituted styrene, vinyltoluene, vinylnaphthalene and combinations thereof . Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene. Styrene may be preferably used as the aromatic vinyl compound.

The vinyl cyanide compound in the mixture to be graft polymerized to the rubbery polymer may be at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof. Preferably, acrylonitrile may be used as the vinyl cyanide compound.

As a preferred example, the rubber-modified vinyl-based graft copolymer containing the functional group of the present invention may be an acrylonitrile-butadiene-styrene graft copolymer (g-ABS) containing an epoxy group or maleic anhydride.

When the rubber-modified vinyl-based graft copolymer of the present invention contains a functional group, it can induce bonding with the polyester resin and reduce the bond between the aromatic vinyl-cyanide vinyl copolymer and the polyester resin relatively. Thereby, there is an advantage that the reaction of the matrix of the thermoplastic resin composition is reduced, the discharge of the gas is reduced, and the fluidity is not lowered, whereby the appearance characteristics are remarkably improved.

The rubber-modified vinyl-based graft copolymer in which the functional group of the present invention is grafted may contain 10 to 40% by weight of the total thermoplastic resin composition. Preferably 15 to 30% by weight. When the content of the rubber-modified vinyl-based graft copolymer in which the functional group is grafted is less than 10% by weight, the compatibility of the thermoplastic resin may be decreased and the impact strength may be lowered. If it is more than 40% by weight, the heat resistance decreases, the decrease of the matrix reaction becomes insignificant, the flow decreases, and the discharge of gas may be intensified.

(B) aromatic vinyl-cyanide Vinyl-based  Copolymer

The aromatic vinyl-cyanide vinyl copolymer according to one embodiment of the present invention is used for improving the mechanical strength, chemical resistance and coloring property in combination with other components in the composition, and is a copolymer of an aromatic vinyl compound and a vinyl cyanide compound Lt; / RTI >

The aromatic vinyl compound and the vinyl cyanide compound may be in a weight ratio of 70:30 to 80:20. More preferably 72: 28 to 76: 24 by weight. When the above range, the chemical resistance and fluidity can be improved.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene, C ₁ to C ₁₀ alkyl-substituted styrene, halogen-substituted styrene, vinyl toluene, vinyl naphthalene, and combinations thereof.

Specific examples of the alkyl-substituted styrene include? -Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, pt-butylstyrene and 2,4-dimethylstyrene.

As the vinyl cyanide compound, at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof may be used.

Specific examples of the aromatic vinyl-cyanide vinyl-based copolymer include copolymers of styrene and acrylonitrile; copolymers of? -methylstyrene and acrylonitrile; Or a copolymer of styrene,? -Methyl styrene and acrylonitrile. A copolymer of styrene-acrylonitrile is preferably used.

In addition, the aromatic vinyl-cyanide vinyl copolymer of the present invention may optionally further include an ethylenic unsaturated monomer. As a result, physical properties such as workability and heat resistance can be improved.

Examples of the ethylenic unsaturated monomer include methyl methacrylate, (C1-C4) alkyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, Aromatic esters of acrylic acid or methacrylic acid such as ethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate, aromatic esters of methacrylic acid such as N-methyl-, N-phenyl and N-cyclohexylmaleimide Substituted maleimide, maleic acid, fumaric acid, itaconic acid and their anhydrides, acrylic acid, methacrylic acid and dicarboxylic acid, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone Nitrogen, and nitrogen-functional monomers such as vinylcaprolactam, vinylcarbazole, vinyl aniline, acrylamide and methacrylamide, and the like, and are limited thereto No.

In addition, the aromatic vinyl-cyanide vinyl copolymer of the present invention may further comprise a maleic anhydride or a nucleus-substituted maleimide monomer. As a result, physical properties such as workability and heat resistance can be improved.

Examples of the nucleus-substituted maleimide monomer include, but are not limited to, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide It is not.

The aromatic vinyl-cyanide vinyl copolymer of the present invention may contain 40 to 60 wt% of the total thermoplastic resin composition. By incorporating in the above range, there is an advantage that the harmony of fluidity, colorability and chemical resistance is excellent.

If the content of the aromatic vinyl-cyanide vinyl copolymer of the present invention is less than 40% by weight, improvement in impact resistance may be insignificant. When the content is more than 60% by weight, fluidity may decrease and color discoloration may occur.

The aromatic vinyl-cyanide vinyl copolymer according to an embodiment of the present invention may have a weight average molecular weight of 80,000 to 120,000 g / mol. And more preferably 90,000 to 110,000 g / mol. In the above range, an appropriate balance of impact strength and workability can be maintained.

(C) a polyester resin

The polyester resin according to one embodiment of the present invention is intended to improve heat resistance, mechanical strength and fluidity in combination with other components in the composition.

The polyester resin of the present invention may be a polyester resin or copolymers thereof obviously known in the art.

The polyester resin of the present invention may have an intrinsic viscosity of 0.5 to 0.5 to 1.1 g / dl, preferably 0.6 to 0.91 g / dl.

The polyester resin is generally selected from the group consisting of terephthalic acid (TPA), isophthalic acid (IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, Naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid Dimethyl terephthalate (DMT), dimethyl isophthalate (DMT), aromatic dicarboxylate (DMT), dimethyl isophthalate (DMT) and the like, which are aromatic dicarboxylates in which an acid is substituted with a dimethyl group, Naphthalene dicarboxylic acid or an alkyl ester of naphthalene dicarboxylic acid or an alkyl ester of naphthalene dicarboxylic acid or an ester of dimethyl-1,2-naphthalate, dimethyl-1,5-naphthalate, dimethyl- Naphthalate, dimethyl-2,3-naphthalate, dimethyl-2,6-naphthalate, dimethyl Naphthalate or a mixture thereof, and ethylene glycol having 2 to 12 carbon atoms as the diol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol , 2,2-dimethyl-1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5- pentanediol, -Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, or a mixture thereof, and the like, but not limited thereto.

As an example, the polyester resin of the present invention may be a polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT) and polycyclohexylene terephthalate ) May be selected.

The polyester resin may be a recycled polyester resin. As an example, it may be a recycled polyethylene terephthalate (PET) polymer. Recycled PET means a product obtained by pulverizing a bottle or sheet made of a PET polymer or re-extruding them. The recycled polyester resin is preferably used in the form of pellets, but the form thereof is not particularly limited.

When a recycled polyester resin is used, there is an advantage of being environmentally friendly.

In addition, the polyester resin may be mixed with the inorganic particles in a conventional manner, depending on the application. Examples of the inorganic particles include, but are not limited to, titanium oxide (TiO ₂ ), silicon dioxide (SiO ₂ ), aluminum hydroxide (Al (OH) ₂ ) and the like.

The polyester resin of the present invention may contain 20 to 50% by weight of the total thermoplastic resin composition. By the inclusion in the above range, there is an advantage that the fluidity and the impact strength are excellent. In addition, there is an advantage that the reaction of the matrix is reduced and the gas generated is reduced, and the appearance characteristics are excellent.

When the content of the polyester resin of the present invention is less than 20% by weight, improvement in impact resistance may be insignificant. When the content is more than 50% by weight, the fluidity and surface properties may decrease.

The thermoplastic resin composition of the present invention may further contain usual additives in addition to the above-described components in accordance with the intended use. Examples of the additives include antimicrobial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, An ultraviolet light absorber, an ultraviolet light absorber, and a mixture thereof.

The thermoplastic resin composition of the present invention can be produced by a known method. For example, each component and additives are mixed with a Henschel mixer, a V blender, a tumbler blender, a ribbon blender, etc., and melt-extruded at a temperature of 150 to 300 ° C using a single screw extruder or a twin screw extruder to produce a pellet . More specifically, extrusion was carried out using a twin-screw extruder having L / D of 20 to 60, Φ = 32 mm and 70 mm under the conditions of a fixed temperature of 240 ° C., a screw rotating speed of 300 to 600 rpm and a self- Whereby a pellet phase can be produced.

According to another embodiment of the present invention, there is provided a molded article produced by molding the above-mentioned thermoplastic resin composition. That is, the thermoplastic resin composition can be used to produce a molded article by various processes such as injection molding, double injection molding, blow molding, extrusion molding, and thermoforming.

The molded article of the present invention can satisfy the following formulas (1) to (3).

10? L? 30 [Formula 1]

50 ≤ IZOD ≤ 80 [Formula 2]

1.0??? E? 3.0 [Formula 3]

In the above Equation 1, L is the black index value according to the ASTM D1925 standard, and IZOD is the IZOD impact strength (kgf · cm / cm) according to the ASTM D256 standard. The change in chromaticity of the specimen due to the retention of 10 minutes in the injection machine at the time of injection.)

The molded article of the present invention is excellent in impact resistance, heat resistance, molding processability and mechanical strength, and the amount of generated gas is reduced due to the reduction of the reaction of the matrix, thereby remarkably improving the appearance characteristics. It can be used effectively as an exterior material.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples.

Property measurement

1) Izod impact strength (unit: kgf · cm / cm)

Measured according to ASTM D256 under notched conditions of 1/8 "thickness.

2) Vicat softening temperature (VST) (unit: ℃)

Was measured under the condition of 5 kgf and 50 占 폚 / hour according to ISO 306 B-50.

3) Blackness (L value)

Lab values were measured using a Konica Minolta CCM instrument according to ASTM D1925.

4) Injection hold △ E and

Pin point molds were used to determine the discoloration of the specimens when the specimens were injected after standing for 10 minutes in an extruder at temperatures of 280 ° C - 270 ° C - 260 ° C - 250 ° C using a Konica Minolta CCM machine .

5) Gas generation during injection stay

Pin point molds were used to visually determine the flow of gas generated on the surface of the specimen when it was injected after staying for 10 minutes in an injection machine at an injection temperature of 280 ° C - 270 ° C - 260 ° C - 250 ° C, Quot; X "when the gas flow is visible, and "& cir &"

The specifications of each component used in the following examples and comparative examples are as follows.

(A) a rubber-modified vinyl-based graft copolymer having a grafted functional group

G-ABS resin having a core-shell shape obtained by emulsion graft-polymerizing 58 wt% of butadiene rubber having an average particle diameter of 0.27 탆, 3 wt% of glycidyl methacrylate, and 39 wt% of styrene and acrylonitrile was used.

(A ') Rubber-modified vinyl-based graft copolymer

G-ABS resin having a core-shell shape obtained by emulsion-graft-polymerizing styrene and acrylonitrile to 58 wt% of butadiene rubber having an average particle diameter of 0.27 mu m was used.

(B1) an aromatic vinyl-cyanide vinyl copolymer

A styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 90,000 g / mol copolymerized from 26% by weight of acrylonitrile and 74% by weight of styrene was used.

(B2) an aromatic vinyl-cyanide vinyl copolymer

A styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 100,000 g / mol copolymerized from 26% by weight of acrylonitrile, 70% by weight of styrene and 4% by weight of glycidyl methacrylate was used.

(C) a polyester resin

Polyethylene terephthalate (PET, trade name: Skypet 1100) manufactured by SK Chemical Co., Ltd., having an intrinsic viscosity of 0.29 dl / g, was used.

(D) Additive

Carbon black (HI BLACK 50L, Korea Carbon Black) having an average particle diameter of 18 nm was used.

[Example 1]

15% by weight of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 55% by weight of an aromatic vinyl-cyanide vinyl copolymer (B1) and 30% by weight of a polyester resin (C) (D) was mixed with 100 parts by weight of a base resin mixed with an ethylene /? - olefin copolymer (B) in an amount of 50% by weight, and the mixture was mixed in a usual mixer, To produce a pellet. The prepared pellets were dried in a dehumidifying dryer at 100 ° C for 4 hours before injection molding, and then specimens were prepared for measurement of physical properties using a 10 oz injection machine at an injection temperature of 230 ° C. The measured physical properties are shown in Table 2 below.

[Example 2]

20 wt% of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 50 wt% of an aromatic vinyl-cyanide vinyl copolymer (B1) and 30 wt% of a polyester resin (C) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Example 3]

25% by weight of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 45% by weight of an aromatic vinyl-vinyl cyanide copolymer (B1) and 30% by weight of a polyester resin (C) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Example 4]

20 wt% of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 45 wt% of an aromatic vinyl-cyanide vinyl copolymer (B1) and 35 wt% of a polyester resin (C) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Example 5]

20 wt% of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 40 wt% of an aromatic vinyl-cyanide vinyl copolymer (B1) and 40 wt% of a polyester resin (C) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Example 6]

10% by weight of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 10% by weight of a rubber-modified vinyl-based graft copolymer (A '), an aromatic vinyl- The same procedure as in Example 1 was carried out except that a base resin in which 50% by weight of the copolymer (B1) and 30% by weight of the polyester resin (C) were used was used and physical properties were measured and shown in Table 2 below.

[Comparative Example 1]

15% by weight of a rubber-modified vinyl-based graft copolymer (A '), 45% by weight of an aromatic vinyl-cyanide vinyl copolymer (B1), an aromatic vinyl-cyanide vinyl copolymer (B2) 10% by weight, and 30% by weight of a polyester resin (C) were used in place of the base resin. The properties were measured and shown in Table 2 below.

[Comparative Example 2]

20% by weight of the rubber-modified vinyl-based graft copolymer (A '), 40% by weight of the aromatic vinyl-cyanide vinyl copolymer (B1), 40% by weight of the aromatic vinyl- 10% by weight, and 30% by weight of a polyester resin (C) were used in place of the base resin. The properties were measured and shown in Table 2 below.

[Comparative Example 3]

25% by weight of the rubber-modified vinyl-based graft copolymer (A '), 35% by weight of the aromatic vinyl-cyanide vinyl copolymer (B1), 25% by weight of the aromatic vinyl-cyanide vinyl copolymer (B2) 10% by weight, and 30% by weight of a polyester resin (C) were used in place of the base resin. The properties were measured and shown in Table 2 below.

[Comparative Example 4]

20% by weight of a rubber-modified vinyl-based graft copolymer (A '), 50% by weight of an aromatic vinyl-cyanide vinyl copolymer (B1) and 30% by weight of a polyester resin (C) The same procedure as in Example 1 was carried out except that a base resin was used, and physical properties were measured and shown in Table 2 below.

[Comparative Example 5]

As shown in the following Table 1, 50% by weight of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted, 20% by weight of an aromatic vinyl-cyanide vinyl copolymer (B1) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Comparative Example 6]

5% by weight of a rubber-modified vinyl-based graft copolymer (A) having a functional group grafted therein, 35% by weight of an aromatic vinyl-vinyl cyanide copolymer (B1) and 60% by weight of a polyester resin (C) Weight% of the base resin was used in place of the base resin, and the properties were measured and shown in Table 2 below.

[Table 1]

[Table 2]

As can be seen from the above Table 2, Examples 1 to 6 according to the present invention show excellent impact strength, ΔE and gas generation rate, and blackness value at the time of injection retention, as compared with Comparative Examples.

Concretely, it is possible to induce the bonding between the rubber-modified vinyl-based graft copolymer in which the functional group is grafted and the polyester resin, to decrease the bonding with the aromatic vinyl-cyanide vinyl copolymer, And the amount of generated gas is decreased.

On the other hand, in Comparative Examples 1 to 3, when an aromatic vinyl-cyanide vinyl copolymer grafted with a functional group was used in place of the rubber-modified vinyl-based graft copolymer grafted with a functional group, the change in chromaticity was increased, .

Further, in the case of Comparative Example 4, the reaction site was not present in the matrix as compared with Example 2, so that the compatibility was remarkably reduced and the impact strength was remarkably decreased.

In the case of Comparative Example 5, the excessive amount of the functional group-grafted rubber-modified vinyl-based graft copolymer decreased heat resistance and gas exhaustion, resulting in deterioration in appearance characteristics. In Comparative Example 6 , The compatibility of the thermoplastic resin composition was reduced, and the impact strength was remarkably reduced.

Therefore, the thermoplastic resin composition according to the embodiment of the present invention contains an optimum content of the rubber-modified vinyl-based graft copolymer in which the functional group is grafted, the aromatic vinyl-cyanide vinyl copolymer and the polyester resin, It is possible to provide a thermoplastic resin composition which is excellent in appearance, appearance and molding processability.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (11)

(A) a rubber-modified vinyl-based graft copolymer in which a functional group is grafted;
(B) an aromatic vinyl-cyanide vinyl copolymer; And
(C) a polyester resin, which is excellent in impact resistance.
The method according to claim 1,
The thermoplastic composition comprises 10 to 40% by weight of a rubber-modified vinyl-based graft copolymer (A) grafted with a functional group, 40 to 60% by weight of an aromatic vinyl-cyanide vinyl copolymer (B) To 50% by weight of the thermoplastic resin composition.
The method according to claim 1,
The rubber-modified vinyl-based graft copolymer in which the functional group is grafted is obtained by copolymerizing 30 to 70% by weight of a rubber-like polymer containing a functional group with 30 to 70% by weight of a mixture of an aromatic vinyl compound and a vinyl cyanide compound Nitrile-butadiene-styrene graft copolymer (g-ABS) having excellent impact resistance.
The method of claim 3,
The rubbery polymer containing the functional group may be prepared by copolymerizing 5 to 60% by weight of isoprene containing at least one functional group selected from a hydroxyl group, an epoxy group, an acryl group, a sulfonyl group, a nitro group, an amide group and a maleic anhydride group, 95% by weight of the total weight of the thermoplastic resin composition.
The method according to claim 1,
The aromatic vinyl-cyanide vinyl copolymer (B) may be selected from a copolymer of styrene and acrylonitrile, a copolymer of? -Methylstyrene and acrylonitrile, and a copolymer of styrene,? -Methylstyrene and acrylonitrile Or less, which is excellent in impact resistance.
The method according to claim 1,
The aromatic vinyl-cyanide vinyl copolymer (B) has a weight average molecular weight of 80,000 to 120,000 g / mol.
The method according to claim 1,
The polyester resin (C) may be at least one selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT) and polycyclohexyleneterephthalate Wherein the thermoplastic resin composition is one or two or more selected from among the thermoplastic resin composition.
The method according to claim 1,
The polyester resin (C) has an intrinsic viscosity of 0.5 to 1.1 g / dl.
The method according to claim 1,
The thermoplastic resin composition may contain at least one selected from the group consisting of an antimicrobial agent, a heat stabilizer, an antioxidant, a releasing agent, a light stabilizer, an inorganic additive, a surfactant, a coupling agent, a plasticizer, a compatibilizer, a lubricant, an antistatic agent, a colorant, , An additive selected from the group consisting of an antistatic agent, an ultraviolet absorber, an ultraviolet screening agent, and a mixture thereof.
A molded article produced from the composition of any one of claims 1 to 9.
11. The method of claim 10,
Wherein the molded article satisfies the following formulas (1) to (3).
10? L? 30 [Formula 1]
50? IZOD? 80 [Formula 2]
1.0?? E? 3.0 [Formula 3]
In the above Equation 1, L is the black index value according to the ASTM D1925 standard, and IZOD is the IZOD impact strength (kgf · cm / cm) according to the ASTM D256 standard. The change in chromaticity of the specimen due to the retention of 10 minutes in the injection machine at the time of injection.)